Process for removing silica from water by way of ion exchange



Apnl 18, 1950 w. w. JUKKOLA ETAL 2,504,695

7 PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE Filed April 14, 1945 9 Sheets-Sheet l r100 t,nu 1,250

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WALFRED w. JUKKOLA, ELLIOTTJ. ROBERTS,

ATTORNEY April 18, 195! w. w. JUKKOLA ETAL 2,504,695

PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE Filed April 14, 1945 9 Sheets-Sheet 2 ATTORNEt p 1950 w. w. JUKKOLA ETAL 2,50

PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE Filed April 14, 1945 9 Sheets-Sheet a v mwwmm 55..

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April 18, 1950 w. w. JUKKOLA EI'AL PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE 9 Sheets-Sheet 4 Filed April 14, 1945 whip-20mm. 2m

9 Sheets-Sheet 5 W. W. JUKKOLA ETAL PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHAWGE Kuhn-E and QVU tn no 3 1 HZ. un w April 18, 1950 Filed April 14, 1945 g 31' O N INVENTOR.

WALFRED W.JUKKOLA,

ELLIOTTJ.RO8ERT8,

ATTORNEY Smw 522196 22.2

April 18, 1950 w. w. JUKKOLA EIAL PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE 9 Sheets-Sheet 6 Filed April 14, 1945 KOFFEEOEPE $20224 mobiwiaumm mwumm tubin- April 1950 w. w. JUKKOLA E'I'AL 2,504,695

PROCESS FOR movmc SILICA mom WATER BY WAY OF ION EXCHANGE 9 Sheets-Sheet '7 Filed April 14, 1945 INVENTOR: WALFRED w. JUKKOLA, ELLIOTT J. ROBERTS,

ATTORNEY April 18, 1950 w. w. JUKKOLA EIAL 4 PROCESS FOR REMOVING SILICA mom WATER BY WAY OF ION EXCHANGE 9 Sheets-Sheet 8 Filed April 14, 1945 mm-SE biz N Q A Q INVENTOR: WALFR'ED w. JUKKOLA ELLIOTT aflosgrns,

ATTORNEY April 1950 w. w. JUKKOLA ETAL 2,504,695 PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE 9 Sheets-Sheet 9 Filed April 14, 1945 :2 T u z ATTORNEY Patented Apr. Id, 1950 PROCESS FOR REMOVING SILICA FROM WATER BY WAY OF ION EXCHANGE Walfred W. J ukkola and Elliott J. Roberts, Westport, Conn., assignors to The Dorr Company, Stamford, Conn., a corporation of Delaware Application April 14, 1945, Serial No. 588,388

8 Claims. (Cl. 210-24) 1 This invention relates to chemical water treatment, and more in particular to the treatment of boiler teed waters for silica removal.

The removal of silica from boiler feed waters has become an important problem in recent years with the trend for higher pressure boilers.

' Under high pressure operating conditions boiler tube failures have often been traced to silicious deposits and trouble is also encountered from these deposits on turbines and in superheaters.

All sources of natural waters contain some dissolved silica and surface waters, a usual occurrence being about 10-15 P.- P. M. SiOz, and in addition usually contain suspended silica. The removal ofrsuspended silica can generally be obtained by coagulation and filtration while chemical processes are necessary for-removal of the colloidal and dissolved silica. Several chemical processes have been developed for this purpose, but nearly all fail to remove the silica to a low enough tolerance and many processes increase the salt content of the water. The silica tolerance or maximum amount of silica allowed in the-boiler reed waters have not been definitely established but as complete as possible a removal of silica is desirable, especially under high pressure boiler operating conditions, because of the greater tendency of the SiOz to form highly insoluble compounds at the higher temperatures and higher pressures. Indeed, silica compounds formed under these conditions may not entirely yield even to scale removal treatment with NaOH.

Some treatment methods may reduce the silica content in the feed water, leaving the balance of $102 to be reacted with NaOH or other well known conditioning chemicals to produce soluble reaction products, for instance by the reaction:

which merely changes the silica to a form less scale-producing, but still presenting the problem of reducing reaction products to a mini- 2 mum concentration so as to avoid their possible corrosive eflect within the boiler system.

Another example of conventional methods of silica removal is what may briefly be called the Magnesia Method. Magnesia (MgO) or magnesium hydroxide (MgOH) added to the water binds the SiOz and precipitates it in some flocculant form removable by filtration; yet this introduces and leaves in the water an excess of the conditioning chemical which in turn increases the water hardness and eventually forms scales in combination with $102. Moreover, an undue excess of conditioning chemical would be required to remove the silica to the extent desired.

A combination method provides for removing firs ne portion of the SiOz by'magnesia treatment, and converting the remainder by NaOH- treatment. v

While feed water free of SiOzand other solutes or salts is attainable by using the condensate of a low pressure boiler as feed water for a high pressure boiler, this invention has for its object to devise a chemical method-for effecting economically the substantially complete removal of S102 from the feed water.

Still other methods of feed water treatment are based on the ion exchange principle which involves contacting the water with ion exchange materials briefly termed ion exchangers or exchangers, such as zeolites, or with those organic or synthetic resinous exchange materials now known as organolites. But any such exchange treatment as now known fails to remove silica as contained in the water.

One such method, whereby ionized solutes can be removed or abstracted from the water, involves the treatment of the water in two sequential exchange stages, namely first with a cation exchanger and then with an anion exchange material, whereby the solutes which are susceptible to such treatment are chemically replaced with the molar equivalent of pure water.

. 3 necticn with the present invention, and it is therefore more fully explained as follows:

The cation exchange material in that instance is saturated with H-ions and therefore also called an H-ion exchange material. It releases H-ions into the water in exchange for the molar equivalents of cations of the solutes. To the extent of that exchange the corresponding acid is formed in the water passing through a bed of H-ion exchange material. The water thus acidified is then passed through a bed of anion exchange material capable of neutralizing the acid in the sense that it releases OH-ions in exchange for the anions of the acid, forming pure 8:0, or else in the sense that the acid molecule as such is adsorbed by the exchanger. The anion exchange material is therefore also known as an acid adsorbing material. In due course of such operation the exchangers lose their exchange capacity which can be restored by regeneration, that is by contact with a suitable regenerant solution which in the case of the H-ion exchange material is a suitable mineral acid such as H2804 or HCl, and in the case of the anion ex change material an alkali such as NazCOa, of suitable concentration.

While the sequential cation and anion exchange treatment will serve to abstract from the water solutes sufllciently strongly ionized,

there are instances or treatment problems in-' volving the use of only the one or the other of these exchange stages. For instances, a water or liquid may be subjected to I-l-ion exchange only, and the resulting liquid be neutralized in some manner other than by anion exchange, or

else a water or liquid already acid may be deacidifled by being contacted with the anion exchange or acid adsorption material.

This invention proposes to effect a substantially complete removal of the silica (SiOz) by subjecting the water to an auxiliary reaction converting the silica in the water into a suitable acid, and then removing that acid from the water by contact with an acid adsorbing or anion exchange material.

When water to be treated passes downwardly through a bed of exchange material, the exhaustion of the bed progresses downwardly from end to end of the bed; that is, the exhausted upper portion of the bed keeps on growing downwardly as the unexhausted portion below it diminishes, unt.l exhaustion has reached the bottom of the bed, at which time regeneration is required. The substantial exhaustion of the exchange capacity of the bed as a whole is indicated by what is known as the breakthrough; that is the appearance of those ions in the efiluent which the exchange material is normally expected to remove. If a regenerant solution is passed through the bed, then regeneration proceeds in a similar progressive fashion, namely from one end of the bed to the other. It can be said that a certain exchange material has a certain inherent exchange capacity as well as inherent regeneration requirements under predetermined operating conditions.

Cation as well as anion exchange materials adapted to function in the manner above indicated, are exemplified by a group of materials now known as organolites because they are of an organic, that is synthetic resinous nature, as distinguished from earlier cation exchange materials, the so-called zeolites, which are of inorganic nature.

In the co-pending patent application of Roberts, Ber. No. 751,882, the water is subjected to auxiliary treatment whereby the silica (SiOz) is converted into a suitable acid. namely one that is removable from the water by ion exchange treatment such as can be effected by means of the aforementioned treatment with a regenerable anion exchange or'acid adsorbing material.

Such auxiliary treatment comprises first subjecting the raw water to de-mineralization treatment by sequential contact with cation and anion exchange materials, which treatment is followed by the silica removal treatment which is based on the concept that the silica must be converted into 'an acid which in turn can be removed by the anion exchange material.

Such auxiliary treatment further comprises reacting the silica (SiOz) with hydrofluoric acid (HF) to the end of producing hydrofluosilieic acid (HzSiFs) which in turn is abstracted from the water by treatment with the anion exchange material.

In such auxiliary treatment a zone or band of HF held by the anion exchange material is allowed or caused to form in the exchange bed, and this zone or band by way of the ion exchange phenomena taking place is in effect caused to progress or shift through the bed ahead of the zone of exhaustion that develops in the bed; that is as the exchange bed becomes progressively exhausted by the acid reaction product (HzSlFe) being taken up, there is maintained in advance of that exhausted portion the band or zone of HF.

In such auxiliary treatment the anion exchange bed following its regeneration with alkali is further conditioned so that it will promptly operate at high eiliciency in effecting SiOz removal. Such conditioning is eflected by passing through the bed a sufllcient quantity of HF solution to establish a desirable HF-zone at the influent end of the bed prior to starting the passage of water through the bed for silica removal.

In such auxiliary treatment a bed of anion exchange material serving to effectuate the auxiliary reaction as well as the removal of the resulting reaction product or acid (HzsiFs), is operated in a manner whereby the fluoride (HF) breakthrough and the subsequent silica breakthrough serve as criteria indicating the degree of exhaustion of the anion exchange bed. I

In one embodiment of such auxiliary treatment the water from which the silica is to be removed is passed through a pair of anion exchange beds operating in series, whereby the first bed can be substantially fully exhausted with a minimum loss of HF. The complete exhaustion of the first bed is possible according to this mode of operation since the HF-zone or band reaching the end of the first bed is eventually further displaced therefrom and without loss transferred to the next fresh bed while water continues passing through these beds. The transfer of the HF-zone is due to-certain affinities of the solutions involved with respect to the exchange material. as will be more fully explained.

Such auxiliary'treatment also provides that to the water having been deionized by sequential anion and cation exchange treatment, there shall be added substantially only the theoretical amount of HF needed for reaction with the SiOz of the water.

Such auxiliary treatment provides for modes of regenerating the anion exchange bed exhausted under these conditions with silica compound, in such a manner that the silicais substantially completely removed from the bed in 5 spite of the tendency of silica to be precipitated on the exchange material. By such modes of regenerating the bed the silica is removed from the bed in a soluble form as eilluent.

Therefore, the anion exchange bed having been saturated or exhausted with HzSiFc is regenerated with an alkali regenerant such as NaOH at an unusually high dilution.

It is oneobject of this invention to reduce the expenditure of regenerant chemicals and more in particular the expenditure of the fluoride. To this end the invention proposes to operate a water treatment-silica removal system in con- Junction with a fluoride recovery system in which to treat the spent regenerant liquors to effect the recovery of fluoride therefrom for re-use in the water treatment system. This invention provides a fluoride recovery system to operate in circuit with the silica removal system. Since the fluoride moves repetitively through that circuit this is herein termed the cyclic silica removal process as distinguished from the process referred to in the aforementioned co-pending patent application and which may be termed the non-cyclic process because it lacks fluoride recovery.

In the Non-cyclic Process the HF or conditioning reagent needed leaves the treatment system or goes to waste, whereas in the Cyclic Process the HF is recovered or isolated from spent regenerant liquors and is reused as a conditioning agent in the further removal of silica from water.

An embodiment of the cyclic process comprises the following phases: (a) the phase of removing the H2S1Fs from the exhausted anion exchange bed in the form of a spent regenerant solution in which it is not too dilute to hamper the isolation therefrom of the silica, and yet in which no silica will precipitate in the bed; (b) the phase of isolating or precipitating and removing the silica from the spent regenerant solution so as to derive a fluoride solution without the silica; (c) the phase of converting the silica-free fluoride solu-' tion into HF-solution to be re-used for conditioning silica-containing water; (at) the phase of conditioning the raw water for the silica removal step; and (e) the phase of silica removal itself in which the anion exchange bed becomes saturated with HzSiFs, which leads back to the phase (a) of the cycle.

In this embodiment of the cyclic process there is coupled with the cycle of the above phases (a) to (e) an auxiliary or intermediate regeneration treatment of the anion exchange bed; that is, the bed having been exhausted with HzSiFs (hydro.- fluo-silicic acid) in the silica removal step, is intermediately treated with-an auxiliary regenerant solution such as NH4F (ammonium fluoride) which yields the silica from the bed as (NHOzSiFc in the spent regenerant solution, the silica thus being in a state of sufficient concentration as well as suflicient solubility. However, since this leaves the bed saturated with HF there follows the second or final regeneration of the bed, namely with a hydroxide or a caustic such as NaOH which allows the fluoride as NaF in the spent solution thus there are derived from the two phases of anion bed regeneration two separate kinds of regenerant liquors containing the silica as (NH4) zSiFs (ammonium-fluo-silicate) and as NaF respectively; therefore, requiring respective separate treatments to produce from them the reagents for re-use in the process. Thus the NaF produces the HF needed for re-use directly through ion exchange substitution of H for the Na. Whereas the (NI-l4) :SiFa is reacted with hydroxide or caustic such as NaOH in what may herein be termed Caustic Precipitation to precipitate the silica while yielding a solution mixure of fluorides such as NaF and NHiF, which mixture in turn can also be converted to HF for re-use by substituting H for the respective cations Na and NH4 in a cation exchange treatment step. However, at least a part of the NH4F needed in the process for intermediate or auxiliary regeneration of the anion exchange bed can be provided by reacting a portion of the available (NH4 )2SiFs with NH4OH in what may herein be termed Ammonia Precipitation. The respective proportions of HF and of NH4F which are thus to be recovered by the respective caustic and ammonia precipitations, depend upon the fluoride balance to be maintained in the cyclic process.

Hence chemical reagents required in this embodiment of the cyclic process are:

HF for conditioning the raw water;

NH4F for the auxiliary regeneration of the anion exchange bed;

NaOH for final regeneration of the anion bed as well as for the Caustic Precipitation of the silica from the spent auxiliary regenerant liquor;

NH4OH for the Ammonia Precipitation of the silica from the spent auxiliary regenerant liquor;

H2SQ4 regenerant solution for maintaining the cation exchange cycle of an auxiliary cation exchange bed.

The total requirements of NaOH, NHiOH, and H2804 are provided from an outside source, whereas HF and NH4F are largely recovered within the process and re-used so that only] small make-up quantities thereof are needed from an outside source. The HF make-up can be provided in the form of NaF since the Na can be replaced with H-ions by cation exchange treatment.

Therefore, one feature of the Cyclic Process lies in the auxiliary regeneration of the exhausted anion exchange bed with NH4F' regenerant solution, and the precipitation of the silica from the resultant spent liquor to yield fluoride solutions for re-use in the process. Since this auxiliary regeneration leaves the bed saturated with HF the bed receives a final regeneration treatment with caustic producing an eflluent fluoride solution convertible by cation exchange into HF for re-use as the initial conditioning reagent for the water.

Other features deal with the manner of the precipitation of the'silica from the eflluent liquors flowing from the anion exchange bed, namely, by Caustic Precipitation and by Ammonia Precipitation. Such features also deal with the manner of recovery and treatment for re-use of the fluoride solutions resulting from such precipitation treatments,

According to one feature, the spent regenerant liquor resulting from the auxiliary regeneration of the anion exchange bed has its silica precipitated by Ammonia Precipitation producing ammonium fluoride solution for re-use as the auxiliary regenerant for the anion exchange bed.

According to another feature, a part of the spent regenerant liquor resulting from the auxiliary regeneration of the anion exchange bed has its silica precipitated by Caustic Precipitation producing a mixture of fluoride solutions convertible into HF solution by cation exchange, for reuse as the initial conditioning reagent for the water, while another part is subjected to Ammonia Precipitation.

Another feature provides for the combined use the anion exchange bed for silica precipitation.

3y treating one portion of the liquor by Caustic Precipitation and another portionby Ammonia Brecipitation there are derived separate fractions of fluoride solutions for re-use, namely ammonium fluoride as one fraction, and a mixture of fluorides as the other fraction. More specifically, this feature provides that a first portion of the spent liquor be subjected to the Caustic Precipitation, whereas a second or subsequent portion of the spent liquor be subjected to the Ammonia Precipitation treatment.

Still another feature provides that the spent eliiuent liquor from the second stage or final regeneration of the anion exchange bed may-be subjected to Caustic Precipitation treatment yielding fluoride solutions which in turn by way of cation exchange treatment will produce HF for re-use as the initial conditioning reagent for the water.

The invention possesses other objects and features of advantage, some of which with the foregoing will be set forth in the following description. In the following description and in the claims, partswill be identified by specific names for convenience, but they are intended to be as generic in their application to similar parts as the art will permit. In the accompanying drawings there has been illustrated the best embodiment of the invention known to us, but such embodiment is to be regarded as typical only of many possible embodiments, and the invention is not to be limited thereto.

The novel features considered characteristic of our invention are set forth with particularity in the appended claims. The invention itself, however, both as to its organization and its method of operation, together with additional objects and advantages thereof, will best be understood from the following description of a specific embodiment when read in connection with the accompanying drawings in which Fig. l is a fiowsheet diagram for the removal of silica according to the Non-Cyclic Process.

Fig. 2 is a schematic showing of the anion exchange bed to illustrate the function of the HF I Fig. 4 is a schematic view of a pair of anion exa change beds operating in series, in the process of being exhausted, to illustrate the transfer of the HF band from a first to a second bed.

Fig. 5 is a fiowsheet diagram for the removal of silica according to the Cyclic Process.

Figs. 6, 7, 8, 9, and represent the fiowsheet of Fig. 5, each figure, however, indicating a different phase of the operating cycle.

Fig. 6 indicates the feedwater treatment phase.

Fig. 7 indicates the auxiliary regeneration phase with fluoride recovery by ammonia precipi: tation Fig. 8 indicates the auxiliary regeneration phase with fluoride recovery by caustic precipitation.

Fig. 9 indicates the auxiliary regeneration phase with fluoride recovery by combination caustic and ammonia precipitation treatment.

Fig. 10 indicates the second or caustic regeneration phase of the anion exchange bed.

Fig. 11 is a chemical fiowsheet, that is a diagram of the Cyclic Process indicating the chemical requirements with ammonia precipitation of the silica.

Fig. 12 is a chemical fiowsheet of the Cyclic Process indicating the chemical requirements with a combination of caustic and ammonia precipitation of the silica.

The fiowsheet diagram of Fig. 1 of the Non- Cyclic Process provides a feedwater tank I 0; that is, a tank for storing the water from which the silica is to be removed, provided with a feedwater supply Ill. The fe'edwater to be subjected to the silica removal treatment of this invention should be substantially free from dissolved salts. Therefore it is desirable to have the ionized solutes substantially removed from the water by a preceding de-ionization treatment, whereby the non-ionized silica is left in the water to be separately removed as by-this process. For the sake of simplicity it will be assumed for this fiowsheet that de-ionized water having the silica left in it is contained in tank I0. A tank I I provides for the storage of the initial conditioning reagent, namely HF solution of a suitable concentration, for admixture to the feedwater. The tank II hasa connection H for supplying HF thereto. A mixing or reaction tank I2 is provided for such conditioning. Flow connections or conduits I3 and I4 lead from the tanks Ill and II respectively to the mixing and reaction tank I2, and are provided with control valves l5 and I6 respectively. A flow connection I! provided with control valve I8 leads from the. reaction tank I2 to a tank or cell I9 containing a bed of known granular anion exchange material 20 also termed acid-adsorbing material, for instance an organic material of the class of synthetic resins sometimes also briefly called exchange resins. The tank I9 will herein be termed the exchange tank or cell. An eiiluent conduit 2|, having a control valve 22, leads from the bottom of the exchange tank I9 and forms a goose neck G presenting a hydraulic column sufliciently high to balance the liquid level in the exchange tank wherebytbe substantial submersion of the exchange bedzfl during operation is insured.

The fe'edwater from tank I0 and the HF solu: tion from tank II are mixed in the. conditioning or reaction tank I2 where silica of the water reacts with HF to produce hydrofluosilicic acid a follows: I

The resulting acid is then removed from the water by contact .with the anion exchange bed 20 through which the water is passed for instance downwardly, thus producing a substantially silica-free eflluent water leaving the bed through an eiliuentconduit 2|.

A storage tank 23 with a supply therefor indicated at 23 contains NaOH for regenerating the anion exchange bed 20 after it has been exhausted with HzSiFs, a supply connection 24 with control valve 25 leading to the exchange tank I9.

While the overall function of the anion bed in removing silica from water dosed with HF lies in the fact that it absorbs H2SiF6 just as it would absorb such acids as H2804, yet the actual chemical mechanism is not so direct, involving transitional reactions. If water containing HzSiFe ispassed through a freshly alkali regenerated bed the effluent is not silica-free until a large quantity of the water has passed. This transitional period may be avoided by applying a quantity of HF to the bed after alkali regeneration beforeany water is passed through the bed i9! eiliuent is silica-free right from the start of the water treatment phase, This band progresses through the exchange bed as the bed becomes pro ressively exhausted. The efficient removal of the silica is due to the presence of this band because it prevents direct contact of the H2S1Fe in the water with the unexhausted (alkali regenerated) portion of the bed. In other words the water always passes through an HF-zone before it contacts the alkali regenerated port on of the bed. The HzsiFe displaces HF from the influent side of the HFj-zone and the displaced HF is reabsorbed by the fresh exchange material at the efliuent side of the zone. In this way the aforementioned progress of theHF-band takes place. Chemically the function of this HF band is that it prevents decomposition of the HzS Fe with consequent formation of silica and leakage thereof with the treated water, which would take place i were the HzSiFs allowed to come in direct contact with the unexhausted portion of the bed which is alkaline in reaction and would therefore cause the aforementioned decomposition of the HzSiFs.

Another important aspect of the formation and effect of the HF-band is that with such an HF- band properly established in the bed, reasonable fluctuations in the HF dosing rate will be equalized as far as the eflluent is concerned, in that the HF band decreases or increases in absorbing these dosing fluctuations. This equalizing effect enables one to dose with the theoretical quantity of- HF without danger of silica leakage into the effluent even though in practical operation precise dosing rates may not be possible.

This condition can be graphically visual zed by reference to the Fig. 2 diagram showing the anion exchange bed ,[N in an intermediate state of exhaustion. Af top zone A saturated with HzSiFa represents the exhausted portion of the bed, while a relatively {shallow intermediate zone or band B is saturated .with HF, and a lower or bottom zone C represents the unexhausted portion of the bed.

Since it is desirable that the HF-band be Drese nt at-=the top df the bed when the feedwater is itarted into the bed such a band or zone may be established prior to starting the operation by adding a sufficient. amount of HF to the top of the. bed, the bed itself having prevously been saturated with OH-ions by regeneration with an alkali solution, for instance NaOH.

The progress of exhaustion of the anion' exchange bed, as indicated by the progress of the -HF-band therethrough, isf raphically shown in Fig. 3 (sub-figures a to e) representing an HF- band D, a zone of exhausted material E, and a zone of unexhausted material F of the bed. These figures incidentally indicate the bed as being about 50%, 70%, 95%, and 100% exhausted, respectively. Consequently the HF i; band is shown in consecutive stages of down- -ward progress through the bed. In the Fig. a

in called the condition of the HF breakthrough of the bed, since the displaced portion of the HF-band now appears in the eilluent water. If the exhaustion is still further continued the HF- band will be completely displaced, leaving the bed substantially totally exhausted or saturated with HzSiFs. this being the Fig. e condition which is substantially incidental to what is, herein termed the silica breakthrough condition of the bed: that is, as the HF-band disappears. the effluent water will then show it in substantially the same condit on as the influent waterwith a portion 01' HzSiFs, a portion of S02 and a portion of HF-since the bed will then have become substantially ineffective.

In order to preserve the HF contained in the HF-band a pair of anion exchange beds maybe operated in series (see Fig. 4). This shows two anion exchange beds B1 and B2 in series, with feedwater entering at W flowing downwardly through bed B1, the eflluent water from that bed being transferred as along line L to the top of bed B: and passing through the same and leaving the bed as silica-free water indicated at S. The beds B1 and B2 are shown in a condition where the bed B1 has been exhausted to the point where a. portion of the HF band has been displaced from the bottom of the bed B1 and appears transferred to the top of the bed'Bz. The bed Bl in this condition comprises an exhausted portion E, and a portion P1 of the HF-band. while the bed B2 comprises a portion P2 of the HF-band and an unexhausted portion U. In this way an HF-band will be established at the top of the second bed at the rate at which it is being displaced at the bottom of the first bed. In this manner the first bed' can be completely exhausted past the silica breakthrough condition, since the HF-band being displaced at the bottom is intercepted and re-established at the top of the second bed. This condition of transferring the exchange function as well as the HF-band from the first bed to the second bed is indicated in Fig. 4 showing a first bed B1 and a second bed B: with a portion of the HF-band still left at the bottom of the first bed and the balance of the HF band having been establ shed at the top of the second bed. In other words, the HF-band desired to be present at the start of the operation of an anion exchange bed can be automatically obtained by using a series of beds if a second regenerated and Washed bed is placed in series with a bed being exhausted shortly before the fluoride breakthrough occurs, the fluoride leakage will be cut by the second bed. Hence, if the first bed is exhausted unt l the silica. in the eiliuent is nearly identical with the silica in the condition the bed is unexhausted and an HF- band has been provided at the'top. In the Fig.

mately halfway down the bed. In the Fig. 0 con- T b condition the HF-band has moved approxifeed-water the HF band will be completely transferred from the bottom of the first to the top of the second bed because the strong bivalent H2SiFo displaces the weak monovalent HF from the one bed to the next.

The following tabulation represents an effluent water analysis during the exhaustion period of the anion exchange bed indicating numerically where the fluoride breakthrough and the silica breakthrough occur respectively, this being the result of a test run on an anion exchange bed 10" deep and 1" in diameter. There is a rough relationship between the degree of exhaustion shown in'the diagram Fig. 3 (sub-figures a to e) which is indicated by the marginal references to these figures in the following Effluent analysis'tabula Volume of Feed Per cent Exhausted to SiOz Fluorides through Bed Silica Breakthrough PH specific P.P.M P. P. M.

liter;

2 a. 3. 1. 2 200, 000 .2 Fig. 30 4 0.1- 1.15 055, 000 .2 0 s 13. 4 1.10 300, 000 .1 0 12 20. 0 1. 05 400,000 .1 o 20.0 ra -35g 1.00 400,000 .1 0 33.0 -,.s we 6.85 0.. 400,000 .1 0 24 -40.0 312 g 1: 0.50 a 300,000 .1 0 2s 41. 0 0: 5 0 5. 20 g 115, 000 .1 0 Fig.

30 50.0 h g s 5.00 E 150,000 .1 .1 02 53.0 gels 4.1 ag, 100,000 .1 .1 30 00.0 g ag g 4.5 3:: 00,000 .1 .2

ac 03.0 4.4 2 05,000 0 .0 v 40 01. 0 I 4. 3 a 41,000 0 -1. 1 Fig. 3c

42 10.0 a s 4.12 20,000 0 1.4 45 15.0 i 4.00 20,000 0 2.0 s 83.0 ms 3.10 11,000 0 2.0 week 220 .35 0.50 0.500 0 5.0 "gen: 53 91.0 a 3.40 4,800 .2 10.5 :83 Fig.3d 00 100.0 I 3.35 4,200 1.0 22.20 E51:

02 104. 0 3. 20 a, 500 2. 0 24. 20 Fig. 30 04 101. 0 3. 20 2,100 4. 0 2s. 20 00 110. 0 a. 20 2, 100 0. 0 32 08 114.0 3.20 1,800 0. 0 40 10 111.0 s. 20 1. 100 12. 0 50 12 120. 0 3. 2o 1. 100 10. 0 55 Alternative modes of initial treatment of the raw water in this process are herein to be considered each of which modes has its advantages depending upon the character and analysis of the raw water; that is the analysis of th solutes or salts other than the silica.

One mode of initial treatment is that which is indicated above in the description of the Noncyclic Method of Silica Removal, namely where the raw water is first subjected to a preliminary or de-ionization treatment not shown per s in the flowsheet of Fig. 1. Such a preliminary treatment comprises passing the water sequentially through a bed of cation exchange material and through a bed of anion exchange material, whereby substantially all inorganic salts or solutes except the silica are abstracted from the water. The chemical mechanism of the de-salting or deionization treatment is well known per se. Suflice it to say that the cation exchange bed, having been regenerated with a suitable mineral acid such as H2SO4 of suitable'concentration, is capable of substituting H-ions for the cations of the salt in the water thereby converting the salt into the corresponding acid. The water leaving the cation exchange bed thus acidified then passes through the anion exchange bed which has been regenerated with a suitable solution of alkali such as NazCOs of suitable concentration, and is therefore capable of adsorbing or abstracting form the water the acid which was produced by the cation exchange bed. It is also said of the anion exchange bed that it substitutes OH-ion for the anion of the acid which has resulted from the cation exchange so that as a net result of these two ion exchange phases the molar equivalent of pure water (HOH or H2O) is substituted for the salt.

The removal of these salts by this preliminary or ole-ionization treatment correspondingly reduces the HF requirement for conditioning the water, inasmuch as otherwise some of the HF would react withthe salts instead of with the silica. Also, having an appreciable Ca content Ca may react with HF to produce sufficient CaF2 which is fairly insoluble causing precipitation trouble in th bed which in turn requires more intense backwashing for precipitate removal; thus the preliminary 0r de-ionization treatment in the conditioning stages of the raw water may be desirable and the expenditures for it warranted.

The HF per se is a corrosive acid and may be produced as needed by treating NaF separately by cation exchange substituting H for Na. As will be seen further below in the description of the Cyclic Process, a cation exchange bed constitutes a part or station in the cyclic operation and serves for passing therethrough NaF' for make-up of and conversion into HF.

When raw water containing, as it usually does, calcium bicarbonate (Ca(HCO'a)2) is subjected to treatment in the cation bed in the de-ionization operation, there is produced free CO2 dissolved in the water as follows:

( ll) 2HX+ Ca (HCOa) 2 CaX2+2H2O+2-CO2 rdinarily this CO2 remains in the water when the same is passed through the acid adsorbin anion exchange bed.

In straight de-ionization operations this CO2 is often removed by aeration. In the present process a limited amount of CO2 in the water does.

not interfere with the emciency of the silica removal, but where excessive amounts are present and the eificiency of the silica removal thereby afiected, the CO2 should be removed by aeration prior to the dosing of the water with HF. 5'

When the anion exchange bed has become exhausted by its adsorption of HzSiF5 it must beregenerated with a solution of alkali such as NazCOa, NaHCOs, or NaOH. Usually 5% concentrated solutions of alkali are used to obtain satisfactory and economical regeneration results. We have found that the anion exchange bed thus exhausted with H2SiF0 did not lend itself to the regeneration with alkali at the usual concentrations, and that the bed could not be successfully regenerated for instance with 5% Na2COz, 4% NaHCOa, or 4% NaOl-I solutions because these reagents caused the precipitation of SiO-z and NazSiFe which subsequently could only be removed by treatment with exceptionally strong (about 10%) alkali solution, which appeared to be prohibitive.

The potential trouble with the precipitation in the bed incident to alkali regeneration may be visualized from the following equations,- with l3 NazCOa, NaHCOa. and NaOH respectively as the regenerant:

For NaaCOa:

(2) NazCOa+HzSiFe- Na:8il"o+Hz0+COa With an excess of N21200: theresulting ,NaaSiFe in the bed is regenerated with, say 4% NaOH reacts further to form a flocculent (S102) -precipitate and '(6NaF) solute, as follows:

() ZNflzCO: NazSiF. 0 siO, 6N8]? 20 0 Under such conditions we have found that, once the silica has precipitated in the bed, it

can be rendered soluble and removed only by a treatment of excess strong NaOH solution (10% NaOH) producing soluble sodium silicate (NazSiOa) as follows:

5) sio, 2Na0H NaiSiO; HIo

However, the precipitation trouble as well as the cost of precipitate removal can be avoided by using the alkali regenerant, such as NaOH, in relatively high dilution, for instance on the order of 0.5%. In other words, when the anion bed has been exhausted with the water containing the HzSiFe, it is regenerated with dilute caustic. The

' strength of the caustic solution that can be used for regeneration is determined by the temperature of the surroundings, and this concentration should not be so high that the concentration of the NazSiFs produced in the regeneration becomes super-saturated and precipitates. Hence, at a temperature of C. the NaOH concentration should be on the order of 0.4% by weight or about 0.1 N. This strength is probably safe down to a temperature slightly below 20 C. If it were possible to maintain a temperature of 40 0., the strength of NaOH could be increased by about because of the increased solubility of NazSiF'e. At 80 C. the concentration would be increased about 100% to about 0.2 N.

The regeneration with the dilute NaOH solution takes place according to the following equation in terms of ion exchange:

(where Y represents the structure of the anion exchange material); or written as a chemical equation:

(6a) H:S1Fe+2NaOH- Na2SlFe+2H2O When using the dilute NaOH solution, the anion bed can be regenerated with four to five equivalents of NaOH per mol of SiOz adsorbed by the bed, the consumption of caustic being some,- what dependent upon the rate of regeneration.

solution, at least 8 equivalents of NaOH would be required per mol of S10: since the reaction that occurs might be expressed by the following equation:

This equation is actually the result of the operation of Equations 4, 4a, and 5. Therefore an additional amount of reagent is consumed in that the silica is removed from the bed as NazSiO: instead of as NazSiF's.

Starting with a freshly alkali regenerated anion exchange bed, in order to efiect the substantially complete removal of the silica from the feedwater at the outset where the feedwater had been dosed with the theoretical quantity" of.

HF, we have conditioned the influent end portion of the bed by adding a small quantity of dilute HF solution to the bed until a small band of HF was formed at the influent end. .The quantity of HF required to produce a satisfactory band of the acid we have found to be about 6 to 10 equivalents of HF per square foot of bed area-.. The anion exchange or acid-adsorbing material used was an organic material of the class of synthetic resinssometimes also briefly' called exchange resins.

As an example, a 10 inch deep bed of granular anion exchange material in a 1" dia. plastic tube was regenerated with caustic and then exhausted I downfiow with solution or feedwater containing P. P. M. SiOz as H2SiFs. The bed adsorbed 131 meq. H2SiFs during exhaustion. After the bed was exhausted it was backwashed to loosen the bed. In this connection the dimension abbreviated as meq. herein stands for milligramequivalent. This dimension will be understood from the following definition:

A gram equivalent of a substance is the weight of a substance displacing or otherwise reacting with-1.008 grams of hydrogen or combining with one-half of a gram-atomic weight, that is 8.00 grams, of oxygen. A meq. or milligram-equivalent is /1000 of a gram-equivalent. one gram-equivalent weight of: H2SiFs=72.04 grams, consequently 1 meq. or milligram-equivalent of H2SiFs=0.072 grams, that is to say this bed has adsorbed 131 0.0'72 grams.

The exhausted bed was regenerated upflow with 3.32 liters of 0.1 N NaOH. A flow rate of 0.5 gal/sq. ft./min. was used during the regeneration. After regeneration the bed was washed with de-ionized water.

In order to. be certain that substantially complete conversion of dissolved silica to HzSiFs in the feedwater would take place, 20 meq. of HF was added to the top of the bed. Then the feedwater containing 60 P. P. M. S102 as HzSiFe was passed through the bed.

The efiiciency of silica removal from the bed with 0.1 N NaOH appeared to depend upon the flow rate used in the regeneration. Based on regeneration efliuent solution analysis, it appeared that when a regeneration flow rate of 0.5 gal./ sq. ft./min. was used, complete removal of $102 was obtained with about 4 mols of NaOH per mol of SiOz while at 1 gal/sq. ft./min. it required about 5 mols per mol of $102 to remove all of the silica from the bed. With the higher flow rate, more of the NazSiFe is converted to NaF.

The capacity of the anion exchange material or exchange resin for HzSiFs with a feedwater-of 60 P. P. M. of silica was about 4.5 meq. per dry Therefore,

81 51516; 35,400 m per cu. ft. to the silica break through. When an excess HF amounting to about breakthrough occurred.

'While it is one of the objects of this invention torecover the fluoride from the spent caustic regeneration liquors by precipitation of the silica therefrom, we have found this to be unfeasible with spent liquors of such high dilution as are necessitated by the conditions described above.

NILF storage tan-k 2'6 and a discharge conne tion f l 21 with valve 28, leading from tank 26 to'the' anion exchange tank I9 for auxiliary regeneratlon of the exchange bed 20'. An eilluent dis charge connection or pipe or header. loam from the'exchange tank I9 and is provided with Under the conditions of the foregoing example the composite spent caustic regeneration liquor contains about 1 gram of silica per liter. From solutions of such low concentrations we have found that the silica could not be precipitated at a pH range of 7.5 to 8.5 without the addition of coagulating reagents such as bone glue. The solubility of the precipitated silica at this pH range in the dilute solutions appeared to be between 0.35 and 0.40 gram SiOz per liter.

herefore, this invention proposes an alternative mode of regeneration whereby a spent liquor of sufficiently high concentration can be derived. This leads to the description of the Cyclic Process presented in the flowsheet diagram of Figs. 5 to 11.

Referring to the key diagram Fig. 5, the nowsheet of the process cycle with fluoride recovery comprises the water treatment system T proper to the left of the dot-and-dash line K and What may herein broadly be termed the fluoride recovery system R to the right of the dot-and-dash line K. The treatment system T comprises a feedwater storage tank I0 having a feedwater supply Illa, an HF storage tank II, a mixing and reaction tank I2 in which the feedwater is dosed with HF, a connection I3 from the feedwater tank I0 and a connection I4 from the HF tank II'j both connections I3 and I4 leading to the mixing and reaction tank I2 and provided with control valves I5 and I6 respectively. A connection or pipe II' having a control valve I8 leads from the reaction tank I2 to a tank I9 containing a bed of granular anion exchange material An efiluent conduit 2| having a control valve 22' forms a goose neck G presenting a hydraulic column sufliciently high to balance the-liquid level in the exchange tank l9 whereby the substantial submersion of the exchange bed 20' during the water treatment operation is insured.

The feedwater from tank I 0' and the HF solution from tank I I' are mixed in the conditioning or reaction tank I2 where silica of the water reacts with HF to produce hydrofluosilicic acid as follows:

The resulting acid is removed from the water by contact with the anion exchange bed 20 through which the water passes for instance downwardly, thus producing a substantially silicafree efiluent water leaving the bed through efllue'nt pipe 2|.

'A storage tank 23' with supply therefor indicated at 23a contains NaOH for regenerating the anion exchange bed 20' after it has been regenerated with NH4F, a supply connection 24 with control valve 25' leading to the exchange a control valve 30. This header 29 has a branch connection 3| with valve 32 leading to a tank 33' representing the Caustic Precipitator, a branch 34 with a valve 35 leading to a tank 36 representing the Ammonia Precipitator, past which a valve 31 is provided in the header 29. At point 38 the header 29 splits into two branches 39 and 40, provided with valves M and 42 respectively. The

branch 39 leads to the storage tank 26 for recovered NH4F. The branch leads to a storage tank 43 for recovered NaF and NH4F in mixture. A discharge pipe or conduit 44 having a valve 45 leads from tank 43 to a tank 46 containing a bed of cation exchange material 41 and will therefore be called the cation exchange tank,

where the mixture of NaF and NH4F from tank 43 is converted to HF.

An efiluent discharge pipe 48 having a valve 49 leads from the cation exchange tank 46 to the HF' storage tank II. age of H2804 solution to serve for the regeneration of the cation exchange bed 41. An H2804 supply for the tank 50 is indicated at 50a. A discharge pipe 5I with valve 52 leads from tank 50 to the cation exchange tank 46.

A branch pipe 24a provided with a valve 241) leads from the NaOH supply pipe 24' to the tank or Caustic Precipitator 33. An additional control valve 240 is provided in the line 24. Fluoride make-up for recovery cycle is shown in the form of an NaF supply 43a for mixed fluoride storage tank.43.

A tank 53 for storing NH40H has a supply 53 and a discharge pipe 54 provided with a con trol valve 55 leading to the tank or Ammonia Precipitator 36.

An outlet connection 56 with control valve 51. from the tank or Caustic Precipitator 33, and an, outlet 58 with a control valve 59 from the tank,

or Ammonia Precipitator 36, both lead into a discharge header 60 feeding a pump GI forcing the' liquorthrough a filter press 62 which has a filtrate outlet connection 63 leading into the header 29 through which it reaches mixedv flu- The filter cake, that is precipitated silica, is removed from the filter press as indicated at 64.

The Cyclic Process according to the flowsheet, of Fig. 5 just described is for the purpose of re covering the fluoride from spent regenerationliquors without appreciable re-cycling of the 1 silica, whereby a considerable reduction in the expenditure of reagent chemicals, especially of HF (or, NaF) may be attained.

The 'Cyclic Process comprises the following main operating phases as represented in the flow-- sheets of Figs. 5, 6, '7, 8, 9 and 10. Each of these figures shows the cyclic diagram as a whole, although a particular operating phase is indicated in each figure by the shading of the tanks or stations involved and by the heavy lines accentuating the corresponding pipe connections involved. a

In this manner Fig. 6 indicates the water treat-- wheresilica in water reacts with HF as follows:

' 6HF-|-SiO HzSiFt-l-2Hz0 A tank 50 is for the stor- Then as the water passes through pipe l1 and through the anion exchange bed '20 the acid (HzSlFo) lS adsorbed by the bed so that a silicafree water passes therefrom as efliuent through the discharge pipe 2|.

The exhaustion or saturation of the bed with HzSiFe proceeds as an HF band moves through the bed in the manner and under conditions described above in connection with the Non-Cyclic Process. The net result of the exhaustion of the bed may be represented by the following equation:

Where Y is the acid absorbing radical of the anion exchange bed.

One explanation of the mechanism of the absorption of the H'zSiFs and of the function of the HF band is as follows: The freshly alkali regenerated exchange material is alkaline in reaction and in addition to absorbing HzSiFe (see Equation 7) would tend to decompose HzSiFs just as any other alkali would do as per equation:

if HzSiFe were allowed to contact freshly alkali regenerated exchange material.

Now, if the HzSlFs solution (i. e. conditioned feedwater) is compelled to pass through a layer or zone of HF absorbed by exchange material before it can contact freshly alkali regenerated exchange material, the reaction 7a is suppressed and the following reaction may be considered to take place:

The exchange material when combined with HF (HF band) is no longer alkaline in reaction, and therefore does not tend to decompose the HzSiFs. Hence this HF band may be considered as a barrier acting to prevent direct contact of the H2SiFs with freshly alkali regenerated exchange material. The HF liberated according to Equation 7b is carried forward through the bed by the water until it .comes in contact with freshly alkali regenerated exchange material, whereupon it will re-form Y-HzFz as follows:

In this way the HF band progresses through the bed and maintains itself as a chemical barrier.

In addition to this function the HF band has an equalizing function in the sense that it permits reasonable fluctuations of the HF-dosing rate without affecting the quality of the finished water. In other words, in spite of such possible fluctuations there is no leakage of silica into the finished water. In case the HF-dosing rate has temporarily dropped below theoretical, this equalizing function of the HF-band can be said to be due to the ability of the HF-band to react with silica as follows:

While this equationappears to be contradictory to Equation 7a, it apparently takes place as long as there is suflicient, excess of Y'HzFz present.

In case the HF-dosing rate has temporarily risen above theoretical, Equation '70 operates and stores HF in the band.

Substantially complete exhaustion of the anion exchange bed may be efiected in a two bed operation, that is with two anion exchange beds operating in series as indicated in Fig. 4.

Then follows the auxiliary regeneration phase (see Fig. 7); that is, after the anion exchange bed 20' has thus been exhausted or saturated, it is backwashed and then the HzSiFa is removed from it by regeneration with a slightly ammoniacal solution of NH4F which may be passed upfiow through the bed. This auxiliary regeneration proceeds according to the equation:

which if written as a purely chemical reaction reads as follows:

In this reaction HFis produced which is adsorbed by the anion exchange bed, the amount of HF produced being equivalent to the HzSiFe originally in the bed.

Any residual regenerant solution in-the bed is then displaced by wash water being passed through the bed.

Coupled with the auxiliary regeneration phase is the recovery of the fluoride from the spent liquor leaving the anion exchange bed from the NHrF'regeneration by treatment to precipitate the silica from the spent liquor.

In order to precipitate the S103 from the spent liquor it can be reacted with a hydroxide such as NaOI-I or NH4OH; therefore, a number of precipitation treatment variations are possible, for instance the entire spent liquor efiluent volume may be treated in the Ammonia Precipitator 36 with NH4OH flowing from tank 53 through pipe 54, or one portion of the eifluent volume may be treated in the Caustic Precipitator while another portion is treated in the Ammonia Precipitator. That is to say, depending upon conditions, the requirements of the fluoride recovery cycle might be satisfied by either the Ammonia Precipitator treatment alone or by the combination of the Caustic and the Ammonia Precipitator treatment. For reasons of clarity of presentation the Caustic and the Ammonia Precipitator treatment are shown in separate diagram Figs. 7 and 8 respectively, whereas a combination of both precipitation phases is represented in Fig. 9.

According to Fig. 8 spent efiluent liquor resulting from the auxiliary regeneration with NH4F passes through efliuent pipe 29 and branch 3i into the Caustic Precipitator 33 where it reacts with NaOH solution flowing from tank 23' through pipes 2t and Ma to tank 33, as follows:

(NHmSiFo 4NaOH 2NH4F 4NaF s10, zrno whereby S102 precipitates, and which reaction is complete at a pH of about 8.0.

The precipitate containing solution passes through header to to pump 5! which forces it through the filter press 62 retaining the S102 precipitate as a fllter cake-and allowing the filtrate and filter washings containing a mixture of NH4F and NaF to pass on to the storage tank 43.

The fluorides thus recovered in tank 43 are passed through the cation exchange bed M. This bed comprises a known granular cation exchange material operating in the hydrogen cycle, for instance an organic material of the class of synthetic resins sometimes also briefly called exchange resins. This bed is saturated with H-ions which substitute for the Na and NH; respectively of the fluorides according to the following exchange equations, producing HF for re-use in the initial conditioning phase of the feedwater:

xx Nmr Nm-x nr 11) xx NaF m-x nr Hence the HF thus recovered'is returned to the HF storage tank ll whence it is again added According to Fig. 7 the NH4F auxiliary regenerant solution from tank 26 passes through pipe 21 to the anion exchange tank l9 and upwardly through the exchange bed 20', while the spent liquor leaves the exchange tank by way of eflluent pipe or header 29, to pass through branch 34 into the Ammonia Precipitator 36 where it reacts with NH4OH flowing from tank 53 through pipe 54 to tank 36, as follows:

whereby S10: precipitates.

, The solution from the Ammonia Precipitator containing the S102 precipitate passes through outlet header 60 and pump 6i into and through the filter or filter press 62 where the silica is retained as filter cake, while the filtrate solution containing the NH4F passes through pipes 63 and 39 to tank 26 for storage and re-use as auxiliary regenerant solution.

The filtrate and strong filter wash solution may thus be reserved to meet NI-IrF requirements of the next operating cycle, while weak wash solution may be sent to tank 43 for conditioning treatment in the cation exchange bed 41. Undue dilution of the auxiliary regenerant solution of NH4F is thus avoided. Maintaining the spent NH4F liquors at higher concentrations means less re-cycling of silica due to the smaller volume of liquor being handled.

Fig. 9 represents theaforementioned combination of caustic precipitation and ammonia precipitation treatment of the spent auxiliary regenerant liquor, which combination will be understood in view of the foregoing description of each of these treatments per se in Figs. '7 and 8 respectively, and in view of the above chemical reactions involved.

That is to say a first portion or volume of the spent auxiliary efliuent liquor volume from the anion exchange bed 20' is sent into and through the Caustic Precipitator 33 while NaOH from tank 23' is used as a precipitant. Then the caustic precipitation is stopped, and a second or subsequent portion which may include some of the wash water displacing the spent liquor from the bed, is sent into and through the Ammonia Precipitator where it reacts with NHiOH as a precipitant from tank 53. The first volume, after having its SiOa precipitate removed from it in passing through the filter press 62, passes to the tank 43 for storing the mixed fluoride NaF and mm. The second volume following the first also passes through filter press 62 to have its $102 precipitate removed, and the filtrate liquor passes to the tank 26 for the storage of NH4F.

The proportions of the first and second volumes of (NHmsm to be thus treated in the respective S102 precipitation steps depends upon the chemical requirements of the process and uponthe fluoride balance to be established in the recovery cycle; that is,-the spent NH4F or (NHQ zsiFe efiluent solution is divided so that about one-half of the silica goes into each of the .preclpitators. The

, first portion or volume of the solution, namely the fraction with the highest silica concentration is sent to the Caustic Precipitator 33, while the remainder is sent to the Ammonia Precipitator. The portion of the spent NH4F regeneration liquor sent to the Ammonia Precipitator 36 will have a lower concentration of silica than the fraction sent to the Caustic Precipitator 33, since an excess of NH4F solution must be used in the regeneration. The actual split will be determined by the ratio of (NH4)2SiFc to NH4F required, since a, fluoride balance must be maintained in the system.

The fluoride make-up may be' introduced into the cycle in the form of NaF which may be added as indicated at 43a in the necessary quantity to the contents of the mixed fluoride storage tank 43.

flow, it removes all or most of the HF by way of the following exchange reaction: (15) Y-HzFz+2NaOH-+Y+2NaF+H2O whereby the bed is left in an alkaline state and thus ready again for,the silica removal treatment of de-ionized feedwater from tank Ill. The efiluent liquor containing the NaF from this regeneration is sent through pipes 29 and 40 to the mixed fluoride storage tank 43.

Prior to starting the feedwater through the bed, an HF band such as described above in connection with the Non-cyclic Process, may be established at the influent end of the bed by the addition of a small but adequate amount of HF to the bed prior to starting, or by stopping the upflow of the caustic solution through the bed short of complete regeneration thereof, that is at a point where a suitable band or zone of HF will be left at the top of the bed, which band will be met by the downflowing feedwater.

In the second or alkali-regeneration stage of the anion exchange bed NH4OH may be substituted for the NaOH as the regenerant solution. We have found the NaOH to be more effective in removing flnal traces of residual silica from the bed, although the effect caused by the incomplete removal of silica can be overcome by the addition of HP to the top of the bed in somewhat greater quantity than required when NaOH is used.

While the spent or NaF-containing solution resulting from the alkali regeneration of the bed is shown in Fig. 10 to be sent directly tostorage tank 43 for treatment in the cation exchange bed 41, if that solution contains an appreciable quantity of silica, it can be sent to the Caustic Precipitator 33 for removal of the silica prior to entering the storage tank 43. The regenerated anion exchange bed 20' is washed to remove the residual free NaOH and NaF from the bed. If an HF-zone hasbeen left at the top of the bed bypreceding 21 upfiow regeneration, the washing may be considered suflicient when the pH of the wash liquid has dropped to the acid side. to the fact that HF will slough off from the HF- zone at the top of the bed.

In the auxiliary regeneration of the anion exchange bed 20 we have found that ammoniacal NHrF with a pH between 8.0 and 8.5 gives good results in the removal of silica from the bed. At this pH range about 3%-5% of the nitrogen is present as free NHiOH. The small amount of H appears to be necessary for releasing all of the HzSiFs from the bed. If the bed is not completely exhausted, some OH- would be present since the anion exchange material will split some of the NHsF to produce OH.

An eiTective procedure for obtaining a silicafree bed, following the auxiliary regeneration with Nit-14F, is to treat it with 110 %-l25% theoretical NaOH. If excess caustic is used, the method of using a sequence of beds should be used when exhausting with feed water, for efiecting an automatic transfer of the HF-zone from one bed to the next.

When using NHrOH instead of NaOl-l in the final regeneration of the anion exchange bed, we have found the most of the silica was removed from the bed as a suspension. We have obtained good results with 300% NHiOH of 3 N. concentration. Although in some instances a small portion of silica failed to be removed, the remaining silica appeared to be very near the tenor feedwater infiuent end of the bed since we found that portion could be tied up in the exchange material by adding a somewhat larger quantity of HF to the top of the bed than was otherwise required. In this way a satisfactory operation was achieved. The Nil-14F solution containing ex= cess NHlOH resulting from this operation may be used as a source of ammonia in the ammonia precipitator.

Where the concentration of silica is low as in the solutions resulting from the caustic treatment of the bed, we have found that the addition of about two pounds of bone glue per 1,000 gallons of solution aids in the precipitation and flocculation of the silica.

We have furthermore found that the filtration property of the precipitated silica depends upon the alkalinity condition during the precipitation. An easily filterable precipitate, that is a white semicrystalline product, can be obtained by adding the spent Nl-lrl solution slowly into a tank containing the theoretical quantity of strong NI-hOl-l solution. In this way most of the silica is precipitated under condition of shock when coming into contact with an excess of the strong ammonia solution. Since this method of precipitation employs the theoretical quantity of NH: it is important in the economy of the process.

Furthermore we have found that an easily filterable silica is obtained by adding a considerable excess of strong ammonia, to the spent NH4F solution, for instance about 25% excess NH; is added during the precipitation. However, this means an additional 25% consumption of H2304 for the regeneration of the cation cells in the conditioning system besides the cost of the excess NH: used. When a considerably lower excess of NH3, for instance only about 5% excess NH; is used in the precipitation, we have found that a clear gelatinous precipitate is formed that filters with difficulty.

We have found that the moisture content of the filter cake depends upon th character of the This criterion is due silica precipitate. When the clear gelatinous precipitate was formed, a filter cake containing only 4.5 to 5% solids was obtained while with the white semi-crystalline precipitate a filter cake containing about 16% solids was obtained. With an average 9 to 10% solids content of the filter cake there would be produced about 10 cubic feet of filter cake per pound mol (60#) of silica.

While HF may be added directly to'the feedwater for conditioning, or NaF may be introduced into the recovery cycle to make up for losses, NH4HF2 represents still another source.

The fluoride recovery cycle is flexible in that single-stage or ammonia precipitation on the one hand, and two-stage or combination caustic and ammonia precipitation on the other hand may be employed.

In practicing the single-stage or ammoniaprecipitation method alone, an analysis of the composite spent NI-IeF solution presents itself as follows:

0.22 N. (NI-I4) 2SiFs and 0.654 N. NH4F In practicing the two-stage or combination caustic and ammonia precipitation method, an analysis of the resulting solutions presents itself as follows:

For the caustic precipitation:

0.40 N. (NH4)2SiFs and 0.25 N. NH lF For the ammonia precipitation:

0.12 N, (NHQ2S1F6 and 0.85 N. NH4F Fig. 11 represents the chemical flowsheet of the cyclic process with ammonia precipitation alone, while Fig. 12 represents the chemical flowsheet with combination caustic and ammonia precpitation.

The chemical requirements or balance of the fluoride recovery cycle are determinable on the basis of 1 mol of silica in the feedwater. Using one pound mol of silica as the basis, it appears (see Equation 1) that six equivalents of HF are required to react with 1 mol of silica to produce two equivalents of HzSiFs. The six equivalents of HF required in the above reaction are obtained by passing through the cation bed d? th mixture of NaF and NHrF solutions collected from the caustic treatment of the anion exchange bed 20' and from neutralization of a portion of the spent NHiF liquor.

The two equivalents of HaSlFs produced in the reaction (Equation 1) are adsorbed by the anion exchange bed 20'. The exhausted bed is regenerated with NH4F. Assuming the regeneration requires 400% theoretical NHiF, then eight equivalents of NH4F are required for the auxiliary regeneration. The resulting spent regenerant liquor will contain two equivalents of (NH4)2SiFe and six equivalents of unreacted NH4F. In the NH4F regeneration reaction (Equation 8a) two equivalents of HF are produced which the bed absorbs.

If the bed is then treated with the two equivalents of NaOH (according to Equation 15), this will produce two equivalents of NaF to be sent to the'mixed fluoride storage .tank 43, furnishing one-third of the required fluoridesfor the feedwater conditioning reaction. The remainder of four equivalents of fluorides must come from the neutralization of the NHiF regeneration efiiuent liquor containing both (NH4)2SlFs and NHrF.

Referring to the chemical flowsheet Fig. 11 for single stage or ammonia precipitation, when a 1 N NH4F solution is used for the regeneration 

1. A PROCESS FOR REMOVING SILICA FROM SIO2-CONTAINING WATER WHICH COMPRISES BRINGING TOGETHER AND REACTING THE SILICA IN THE WATER WITH A QUANTITY OF HYDROFLUORIC ACID TO PRODUCE HYDROFLUOSILICIC ACID, ADSORBING THE ACID BY PASSING THE WATER THROUGH A BED OF ACID-ADSORBING ANION EXCHANGE MATERIAL, FLOWING THROUGH THE BED IN SUBMERGENCE A SOLUTION OF AMMONIUM FLUORIDE WHEREBY HYDROFLUORIC ACID REPLACES HYDROFLUOSILICIC ACID IN THE BED AND WHEREBY THERE PASSES FROM THE BED A FLUOSILICATE SOLUTION ADAPTED TO 